Arylamino anthraquinone dyestuffs and process for their manufacture



Patented Dec. 7, 1937 UNITED. STATES PATENT OFFICE 7 I ARYLAMINO ANTHRAQUINONE DYESTUFFS AND PROCESS FOR THEIR MANUFACTURE Albin Peter,Basel, Switzerland, assignor to the firm Chemical Works formerly Sandoz,Basel,

Switzerland No Drawing. Original application March 13,

1935, Serial No. 10,938. Divided and this application December 28, 1936,Serial No. 117,973.

1 In Germany March 21, 1934 8 Claims.

wherein X represents methyl or ethyl, Y represents methyl, ethyl orhalogen and Z represents hydrogen or methyl, with such anthraquinonederivatives that contain at least two groups replaceable by an aromaticamine.

The aromatic amines useful for the production of the new anthraquinonedyestufis are for example 1-amino-2,4,6-trimethylbenzene, l-amino- 252,6- dimethylbenzene, l-amino -2,4- dimethyl -6- bromobenzene, l-amino-6- ethyl -2,4- dimethylbenzene or the like.

The anthraquinone derivatives which can be used in the present processare for example the no 1,4- or 1,5- or1,8-or 1,7- or1,6-dichlro-anthraquinones, further the derivatives ofa-hydroxyanthraquinones, such as the leuco-1,4-dihydroxyanthraquinone.

The condensation of the anthraquinone derivatives with the aromaticbases of the above cited configuration is generally carried out inpresence of a solvent and a catalyst, at temperatures between 50 and 250C., and in an open or in a closed vessel. As suitable solvents thefollowing ones, or mixtures thereof, can be used: water, ethanol,methanol, chlorobenzene, nitrobenzene, dimethylanili-ne,xphenol,glacialacetic acid and the o-o-disubstituted aromatic bases themselves, whenthey are used in excess.

As catalyst generallyfinely divided copper or copper salts are used, butit is also possible to carry out the condensation in absence of copper.Sometimes it is advantageous to carry out the condensation in an inertatmosphere, for example in nitrogen or carbon dioxide atmosphere,preferably under addition'to the reactionmixture of acid-binding agents,such as sodium-, potassiumor ammonium-acetate, sodiumorpotassiumcarbonate or, bicarbonate, soap and the like.

The condensation products obtained according to the present process are,when they are not sulphonated, valuable compounds for the dyeing oflacquers, such as nitro-cellulose lacquers, or of cellulose esters andethers.

In order to prepare water-soluble dyestuffs from water-insolublecondensation products these are sulphonated with sulphuric acid orfuming sulphuric acid of an. appropriate concentration of S03 or withchlorosulphonic acid, whereby one or more sulphonic acid groups will beintroduced into the aryl or into the'anthraquinone nucleus.

The dyestuffs prepared according to the process cited above are, whenthey are soluble in water, very valuable dyestuffs for animal fibressuch as wool and natural silk. The use of the aromatic aminessubstituted in both ortho-positions to the amino group allows to obtaindyestufis with very pure and brilliant shades and 'of excellent fastnessproperties.

One object of the present invention is, therefore, the anthraquinonedyestuffs containing in their molecule at least two groups Y V V -NH Zwherein X represents methyl or ethyl, Y represents halogen, methyl orethyl and. V represents hydrogen or a sulpho group, and Z representshydrogen or methyl.

Another object of the present invention is the process for themanufacture of anthraquinone dyestuffs, consisting in condensing onemolecule of an anthraquinonederivative with at least two molecules: ofthe above listed o-o-disubstituted aromatic amines of the benzeneseries.

Still another object of the present invention is the process for thecondensation of anthraquinone derivatives with the o-o-disubstitutedaromatic amines of the benzene series, consisting in performing thecondensation in presence of solvents or diluents and catalysts, such ascopper or copper salts, and in presence of acid-binding agents and attemperatures between 50 and 250 C.

Still another object of the present invention is thecondensationprocess, wherein as acid-binding agents an excess of theo-o-disubstituted aro matic amines of the benzene series is used.

Still another object of the present invention is the process oftransforming the water-insoluble condensation products of anthraquinonederiva tives with the o-o-disubstituted aromatic amines intowater-soluble dyestufis by treating them with sulphonating agents, suchas sulphuric acid,

fuming sulphuric acid or chlorosulphonic acid.

The following example, without being limitative, illustrates the presentinvention, the parts being by weight.

' Example 20 parts of 1,4-dichloro-anthraquinone, 18. parts of potassiumacetate, 0,1 part of copper powder and 70 parts of1-amino2,6-dimethylbenzene are heated to 1'70-l80 C., until the shade ofthe reaction mixture does nomore change and 7 after cooling down toabout 100 C., the condensation product is isolated.

By sulphonating the base with Weak oleum at 40 C. a dyestufi is obtainedwhich dyes wool brilliant reddish-blue shades of excellent fastness tolight, milling, perspiration and'chromine. Its formula is:

CHa

o0 s o H Oi CH3 3 V cm HN CH:

By replacing the 1-.amino-2z6-dimethylbenzene by1-amino-2:4:fietrimethylbenzene, a similar dyestuff will be obtained. a

By using ,1:5-dichloro-anthraquinone instead of the 1:4-compound, areddyestufi will be obtained, which gives on wool dyeings of very goodiastness to milling and to light.

What I claim is:

1. A process for the manufacture of anthraquinone dyestufis, consistingin condensing anthraquinone derivatives containing in oc-POSition twomembers. of the ,group consisting of halogen and hydroxy with anaromatic amine of the general formula wherein X stands for a member ofthe group consisting of methyl and ethyl, Y stands for a member of thegroup consisting of methyl, ethyl and halogen and Z stands for a memberof the group consisting of hydrogen and methyl. 7

2. A process for the manufacture of anthraquinone dyestuffs, consistingin condensing anthraquinone compounds containing at least two halogenatoms in a-position with an aromatic amine of the general formula 3. Aprocess for the manufacture of anthraquinone dyestuifs, consisting incondensing 1,4- dichloro-anthraquinone with1-amino-2,4,6-trimethylbenzene and sulphonating the base therebyobtained with sulphuric acid.

4. A process for the manufacture of anthraquinone dyestufis, consistingin condensing 1,4- 'dichloro-anthraquinone with1-amino-2,6-dimethylbenzene and sulphonating the base thereby obtainedwith sulphuric acid.

5. The anthraquinone dyestuffs of the general formula V 2 NH 2 ;-z

0:00 Y S 01H NH 7 Z wherein x stands'for a member of the groupconsisting of methyl and ethyl, Y stands for a member of the groupconsisting of halogen, methyl and ethyl and Z, represents a member ofthe group consisting of hydrogen and methyl,

said dyestufis consisting in drystate dark powders soluble in water witha blue or bluish-red coloration and dyeing animal fibres blue tobluishred shades.

7. The anthraquinone dyestufi of the formula CH: V r S OaH HN on. O/ H.7 CH 7 7 oo s cm N CH:

8. The anthraquinone dyestufl of the formula [I H. a on; C 0

ALBIN PE ER- soil

